JPH08170020A - Fluorine-containing siloxane o/w-type emulsion composition - Google Patents
Fluorine-containing siloxane o/w-type emulsion compositionInfo
- Publication number
- JPH08170020A JPH08170020A JP33432994A JP33432994A JPH08170020A JP H08170020 A JPH08170020 A JP H08170020A JP 33432994 A JP33432994 A JP 33432994A JP 33432994 A JP33432994 A JP 33432994A JP H08170020 A JPH08170020 A JP H08170020A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- water
- component
- composition
- containing siloxane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は離型性、潤滑性に優れた
含フッ素シロキサンを含む水系エマルジョンに関するも
のである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous emulsion containing a fluorine-containing siloxane having excellent releasability and lubricity.
【０００２】[0002]
【従来の技術】下記一般式（１）：2. Description of the Related Art The following general formula (1):
【０００３】[0003]
【化２】 Embedded image
【０００４】（式中、Ｒｆはパーフルオロアルキル基又
はパーフルオロオキシアルキル基であり、Ｍｅはメチル
基であり、Ｌは０又は１の整数であり、ｍは４〜２０の
整数であり、ｎは１〜３の整数である）で表される含フ
ッ素シロキサンは、特開平３−２５１８９号公報に開示
されており、離型性、潤滑性等に優れている。また、こ
のシロキサンは水不溶性であるため、これを希釈、或い
は洗浄するときには、有機溶剤を用いる。しかしなが
ら、有機溶剤には、毒性や引火性を持つものが多く安全
衛生上問題がある。また、洗浄剤や切削油剤のように水
系で使用され、優れた潤滑性等を発揮する添加剤が望ま
れている。(In the formula, Rf is a perfluoroalkyl group or a perfluorooxyalkyl group, Me is a methyl group, L is an integer of 0 or 1, m is an integer of 4 to 20, and n is n. Is an integer of 1 to 3), and the fluorine-containing siloxane is disclosed in JP-A-3-25189, and is excellent in mold releasability and lubricity. Further, since this siloxane is insoluble in water, an organic solvent is used when diluting or washing it. However, many organic solvents are toxic and flammable, which poses a safety and health problem. Further, additives such as detergents and cutting oils that are used in a water system and exhibit excellent lubricity are desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、低粘
度でかつ保存安定性、希釈安定性に優れると同時に、取
扱において、作業安全性、及び環境保全性に優れ、水系
で使用する場合にも、優れた撥油性、離型性、潤滑性、
洗浄性を発揮する含フッ素シロキサン水中油滴型組成物
を提供することにある。The object of the present invention is to have a low viscosity and excellent storage stability and dilution stability, and at the same time, it is excellent in work safety and environmental conservation in handling and is used in an aqueous system. Also has excellent oil repellency, releasability, lubricity,
It is an object of the present invention to provide a fluorine-containing siloxane oil-in-water type composition exhibiting detergency.
【０００６】[0006]
【課題を解決するための手段】本発明は、（Ａ）下記一
般式（１）：The present invention includes (A) the following general formula (1):
【０００７】[0007]
【化３】 Embedded image
【０００８】（式中、Ｒｆはパーフルオロアルキル基又
はパーフルオロオキシアルキル基であり、Ｍｅはメチル
基であり、Ｌは０又は１の整数であり、ｍは４〜２０の
整数であり、ｎは１〜３の整数である）で表される含フ
ッ素シロキサン、（Ｂ）界面活性剤、及び（Ｃ）水を含
有する含フッ素シロキサン水中油滴型組成物である。以
下、本発明を詳細に説明する。(In the formula, Rf is a perfluoroalkyl group or a perfluorooxyalkyl group, Me is a methyl group, L is an integer of 0 or 1, m is an integer of 4 to 20, and n is n. Is an integer of 1 to 3), and a fluorine-containing siloxane oil-in-water composition containing a fluorine-containing siloxane, (B) a surfactant, and (C) water. Hereinafter, the present invention will be described in detail.
【０００９】（Ａ）成分の含フッ素シロキサン 本発明に用いる（Ａ）成分の含フッ素シロキサンは、前
記一般式（１）で表され、式中、Ｒｆで示されるパーフ
ルオロアルキル基としては、例えば、下記一般式： ＣP Ｆ2P+1− （式中、ｐは４〜１２、好ましくは、６〜９の整数であ
る）で表される直鎖状又は分岐状の基であり、具体的に
は、例えば、ＣＦ3 ＣＦ2 ＣＦ2 ＣＦ2 −、ＣＦ3 ＣＦ
2 ＣＦ2 ＣＦ2 ＣＦ2 −、ＣＦ3 （ＣＦ2 ）4 ＣＦ
2 −、ＣＦ3 （ＣＦ2 ）5 ＣＦ2 −、ＣＦ3 （ＣＦ2 ）
6 ＣＦ2 −、ＣＦ3 （ＣＦ2 ）7 ＣＦ2 −、ＣＦ3 （Ｃ
Ｆ2 ）8 ＣＦ2 −、（ＣＦ3 ）2 ＣＦＣＦ2 −、（ＣＦ
3 ）2 ＣＦＣＦ2 ＣＦ2 −、（ＣＦ3 ）2 ＣＦＣＦ2 Ｃ
Ｆ2 ＣＦ2 −等を挙げることができ、中でも好ましいの
は、ＣＦ3 （ＣＦ2 ）4 ＣＦ2 −、ＣＦ3 （ＣＦ2 ）5
ＣＦ2 −、ＣＦ3 （ＣＦ2 ）6 ＣＦ2 −、ＣＦ3 （ＣＦ
2 ）7 ＣＦ2 −である。 Fluorine-Containing Siloxane of Component (A) The fluorine-containing siloxane of the component (A) used in the present invention is represented by the general formula (1), and in the formula, examples of the perfluoroalkyl group represented by Rf include the following general formula: C P F 2P + 1 - ( wherein, p is 4 to 12, preferably an integer of 6 to 9) is a linear or branched group represented by specific the, for example, CF 3 CF 2 CF 2 CF 2 -, CF 3 CF
2 CF 2 CF 2 CF 2 - , CF 3 (CF 2) 4 CF
2 -, CF 3 (CF 2 ) 5 CF 2 -, CF 3 (CF 2)
6 CF 2 −, CF 3 (CF 2 ) 7 CF 2 −, CF 3 (C
F 2) 8 CF 2 -, (CF 3) 2 CFCF 2 -, (CF
3 ) 2 CFCF 2 CF 2 −, (CF 3 ) 2 CFCF 2 C
F 2 CF 2 — and the like can be mentioned, and among them, CF 3 (CF 2 ) 4 CF 2 — and CF 3 (CF 2 ) 5 are preferable.
CF 2 -, CF 3 (CF 2) 6 CF 2 -, CF 3 (CF
2 ) 7 CF 2 −.
【００１０】前記一般式（１）中、Ｒｆで示されるパー
フルオロオキシアルキル基としては、例えば、下記一般
式： Ｆ−〔Ｃ（ＣＦ3 ）ＦＣＦ2 Ｏ〕s Ｃ（ＣＦ3 ）Ｆ− （式中、ｓは１〜１０、好ましくは２〜４の整数であ
る）で表される基などの、例えば、炭素原子数５〜３
５、好ましくは８〜１５の直鎖状又は分岐状ものであ
り、具体的には、例えば、ＣＦ3 ＣＦ2 ＣＦ2 ＯＣ（Ｃ
Ｆ3 ）Ｆ−、ＣＦ3 ＣＦ2 ＣＦ2 ＯＣ（ＣＦ3 ）ＦＣＦ
2 ＯＣ（ＣＦ3 ）Ｆ−、ＣＦ3 ＣＦ2 ＣＦ2 Ｏ〔Ｃ（Ｃ
Ｆ3 ）ＦＣＦ2 Ｏ〕2 Ｃ（ＣＦ3 ）Ｆ−、Ｆ−〔Ｃ（Ｃ
Ｆ3 ）ＦＣＦ2 Ｏ〕3 Ｃ（ＣＦ3 ）Ｆ−、Ｆ−〔Ｃ（Ｃ
Ｆ3 ）ＦＣＦ2 Ｏ〕4 Ｃ（ＣＦ3 ）Ｆ−等を挙げること
ができ、中でも好ましいのは、ＣＦ3 ＣＦ2 ＣＦ2 ＯＣ
（ＣＦ3 ）Ｆ−、ＣＦ3 ＣＦ2 ＣＦ2 ＯＣ（ＣＦ3 ）Ｆ
ＣＦ2 ＯＣ（ＣＦ3 ）Ｆ−、ＣＦ3 ＣＦ2 ＣＦ2 Ｏ〔Ｃ
（ＣＦ3 ）ＦＣＦ2 Ｏ〕2 Ｃ（ＣＦ3 ）Ｆ−である。In the general formula (1), examples of the perfluorooxyalkyl group represented by Rf include the following general formula: F- [C (CF 3 ) FCF 2 O] s C (CF 3 ) F- ( In the formula, s is an integer of 1 to 10, preferably 2 to 4) such as a group represented by, for example, 5 to 3 carbon atoms.
5, preferably 8 to 15 linear or branched, and specifically, for example, CF 3 CF 2 CF 2 OC (C
F 3) F-, CF 3 CF 2 CF 2 OC (CF 3) FCF
2 OC (CF 3) F-, CF 3 CF 2 CF 2 O [C (C
F 3) FCF 2 O] 2 C (CF 3) F-, F- [C (C
F 3) FCF 2 O] 3 C (CF 3) F-, F- [C (C
F 3) FCF 2 O] 4 C (CF 3) F- like. Of these, preferred are, CF 3 CF 2 CF 2 OC
(CF 3) F-, CF 3 CF 2 CF 2 OC (CF 3) F
CF 2 OC (CF 3) F- , CF 3 CF 2 CF 2 O [C
(CF 3) FCF 2 O] 2 C (CF 3) is F-.
【００１１】前記一般式（１）中、Ｍｅはメチル基であ
り、Ｌは０又は１の整数であり、ｍは４〜２０、好まし
くは８〜１２の整数であり、ｎは１、２又は３である。
また、（Ａ）成分の含フッ素シロキサンは、２５℃にお
いて液体のもの、例えば、１〜５０ｃＳｔのものが好ま
しく、さらに好ましくは、粘度が６〜３０ｃＳｔのもの
である。（Ａ）成分の含フッ素シロキサンは、例えば、
特開平３−２５１５８９号に開示される方法で製造する
ことができる。本発明の組成物における（Ａ）成分の含
フッ素シロキサンの含有率は、通常、１０〜９０重量
％、好ましくは、２０〜７０重量％であり、さらに好ま
しくは、３０〜６０重量％である。なお、この含有率が
少な過ぎると、含フッ素シロキサンによる潤滑性等の効
果が低下する上に、組成物の容量が大きくなるため、輸
送等の点でも不経済になる場合があり、多過ぎると乳化
性組成物の製造が困難になると共に組成物の粘度が高く
なるため、取り扱いが困難になるなど作業性の面で不利
になる場合がある。In the general formula (1), Me is a methyl group, L is an integer of 0 or 1, m is an integer of 4 to 20, preferably 8 to 12, and n is 1, 2 or It is 3.
The fluorine-containing siloxane as the component (A) is preferably liquid at 25 ° C., for example, 1 to 50 cSt, and more preferably 6 to 30 cSt. The fluorine-containing siloxane as the component (A) is, for example,
It can be produced by the method disclosed in JP-A-3-251589. The content of the fluorine-containing siloxane as the component (A) in the composition of the present invention is usually 10 to 90% by weight, preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. If the content is too low, the effects of the fluorine-containing siloxane such as lubricity are deteriorated, and the volume of the composition is increased, which may be uneconomical in terms of transportation and the like. Since the production of the emulsifiable composition becomes difficult and the viscosity of the composition becomes high, it may be difficult to handle, which is disadvantageous in terms of workability.
【００１２】（Ｂ）成分の界面活性剤 本発明に用いる（Ｂ）成分の界面活性剤としては、乳化
剤として用いることができるものであれば特に制限はな
く、例えば、ノニオン界面活性剤、カチオン界面活性
剤、アニオン界面活性剤、両性界面活性剤等を挙げるこ
とができる。中でも好ましいのは、ノニオン界面活性剤
である。前記ノニオン界面活性剤としては、例えば、ポ
リオキシエチレン高級アルコールエーテル、ポリオキシ
エチレンアルキルフェニルエーテル、ポリオキシエチレ
ンソルビタン脂肪酸エステル、ソルビタン脂肪酸エステ
ル、グリセリン脂肪酸エステル等を挙げることができ
る。これらは単独で、或いは２種以上を組み合わせて用
いることができる。 Component (B) Surfactant The component (B) surfactant used in the present invention is not particularly limited as long as it can be used as an emulsifier, and examples thereof include nonionic surfactants and cationic interfaces. Examples thereof include activators, anionic surfactants and amphoteric surfactants. Of these, nonionic surfactants are preferable. Examples of the nonionic surfactants include polyoxyethylene higher alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, and glycerin fatty acid esters. These may be used alone or in combination of two or more.
【００１３】また、本発明に用いる界面活性剤として特
に好適なものは、例えば、グリフィンの式によるＨＬＢ
値（親水親油バランス値）が１０〜１８、好ましくは１
２〜１５のノニオン界面活性剤である。なお、２種以上
のノニオン界面活性剤を用いる場合のＨＬＢ値は、それ
ぞれのノニオン界面活性剤のＨＬＢ値の加重平均であ
る。本発明の組成物における（Ｂ）成分の界面活性剤の
含有率は、通常、１〜５０重量％、好ましくは、２〜１
０重量％であり、さらに好ましくは、３〜５重量％であ
る。なお、この含有率が少な過ぎると、乳化組成物の安
定性が低下する場合があり、多過ぎると、組成物の粘度
が高くなるため、取り扱いが困難になるなど作業性の面
で不利になる場合がある。Further, a particularly suitable surfactant used in the present invention is, for example, HLB according to the Griffin's formula.
Value (hydrophilic / lipophilic balance value) is 10 to 18, preferably 1
2 to 15 nonionic surfactants. The HLB value when two or more nonionic surfactants are used is a weighted average of the HLB values of the respective nonionic surfactants. The content of the component (B) surfactant in the composition of the present invention is usually 1 to 50% by weight, preferably 2-1.
It is 0% by weight, more preferably 3 to 5% by weight. If the content is too low, the stability of the emulsified composition may decrease, and if it is too high, the viscosity of the composition increases, which is disadvantageous in terms of workability such as difficulty in handling. There are cases.
【００１４】（Ｃ）成分の水 本発明に用いる（Ｃ）成分の水としては、特に制限はな
く、純水を好適に用いることができる。本発明の組成物
における（Ｃ）成分の水の含有率は、組成物中の（Ａ）
成分、（Ｂ）成分を除いた残部とすればよいものである
が、通常、９〜８９重量％、好ましくは、２９〜７９重
量％であり、さらに好ましくは、３９〜６９重量％であ
る。なお、この含有率が少な過ぎると、乳化組成物の粘
度が高くなり、取り扱いが困難であるなど作業性の面で
不利になる場合があり、多過ぎると、組成物の容量が大
きくなり、輸送等の点で不経済になる場合がある。[0014] As the (C) used in the components of the water present invention component (C) of water is not particularly limited, it is possible to use pure water suitably. The water content of the component (C) in the composition of the present invention is (A) in the composition.
The rest is the component and the component (B), but the content is usually 9 to 89% by weight, preferably 29 to 79% by weight, and more preferably 39 to 69% by weight. If the content is too low, the viscosity of the emulsified composition will be high, which may be disadvantageous in terms of workability such as difficult handling, and if it is too high, the volume of the composition will increase, and the composition will be transported. In some cases, it becomes uneconomical.
【００１５】含フッ素シロキサン水中油滴型乳化組成物 本発明の組成物は、（Ａ）成分のフッ素ポリシロキサン
を、（Ｃ）成分の水中に、（Ｂ）成分の界面活性剤とと
もに分散させることにより得ることができる。前記フッ
素ポリシロキサンを水中に分散させる方法としては、ホ
モミキサー、コロイドミル、高圧ホモジナイザー等の高
剪断乳化分散機を用いる方法を挙げることができるが、
この際、分散機に仕込んだ（Ｃ）成分の水に、（Ａ）成
分のフッ素ポリシロキサンと、（Ｂ）成分の界面活性剤
との混合物を徐々に投入しても、或いは分散機に仕込ん
だ（Ｂ）成分の界面活性剤と（Ｃ）成分の水との混合物
中に、（Ａ）成分のフッ素ポリシロキサンを徐々に投入
しても、あるいは、分散機に仕込んだ（Ａ）成分のフッ
素ポリシロキサンと（Ｂ）成分の界面活性剤との混合物
中に、（Ｃ）成分の水を徐々に投入してもよい。なお、
本発明の組成物に、更にｐＨ緩衝剤、防腐剤、鎮静剤、
浸透剤などを適宜添加配合しても良い。本発明の組成物
は、水性塗料用添加剤、建築用撥水剤、ペインタブル性
を有する離型剤、水性潤滑剤シリコンウェハー切削油
剤、消泡剤等に応用できる。 Fluorine-Containing Siloxane Oil-in-Water Emulsion Composition In the composition of the present invention, the fluoropolysiloxane of the component (A) is dispersed in the water of the component (C) together with the surfactant of the component (B). Can be obtained by Examples of the method for dispersing the fluoropolysiloxane in water include a method using a high shear emulsifying disperser such as a homomixer, a colloid mill and a high pressure homogenizer.
At this time, the mixture of the component (A) component fluoropolysiloxane and the component (B) surfactant is gradually added to the component (C) water charged in the disperser, or the mixture is prepared in the disperser. If the fluoropolysiloxane of the component (A) is gradually added to the mixture of the surfactant of the component (B) and the water of the component (C), or if the component (A) is charged in the disperser. Water as the component (C) may be gradually added to the mixture of the fluoropolysiloxane and the surfactant as the component (B). In addition,
The composition of the present invention further comprises a pH buffer, a preservative, a sedative,
A penetrant or the like may be appropriately added and blended. The composition of the present invention can be applied to additives for water-based paints, water repellents for construction, mold release agents having paintability, water-based lubricants silicon wafer cutting oils, defoamers and the like.
【００１６】[0016]
【実施例】以下、実施例によって本発明を更に詳述する
が、本発明はこれによって限定されるものではない。な
お、以下の例中のＨＬＢ値は全てグリフィンの式による
値を意味する。実施例１ ２００ｍｌプラスチックビーカーに（Ｂ）成分として、
ＨＬＢ値が１６．９のポリオキシエチレンラウリルエー
テル５．４ｇと、ＨＬＢ値が９．６のポリオキシエチレ
ンラウリルエーテル３．６ｇとを仕込み、水３０．０ｇ
と共にホモミキサーでよく混合した。この中に、（Ａ）
成分として下記式：The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. All HLB values in the following examples mean values according to Griffin's formula. Example 1 As a component (B) in a 200 ml plastic beaker,
Charge 5.4 g of polyoxyethylene lauryl ether having an HLB value of 16.9 and 3.6 g of polyoxyethylene lauryl ether having an HLB value of 9.6, and add 30.0 g of water.
Well mixed with a homomixer. In this, (A)
The following formula as an ingredient:
【００１７】[0017]
【化４】 [Chemical 4]
【００１８】で表される含フッ素シロキサン９０．０ｇ
を徐々に加えて、ホモミキサーで均一に混合した。得ら
れた混合物を５００ｍｌプラスチックビーカーに移し、
これに水１７１．０ｇを徐々に添加して分散液を得た。
次いで、これを高圧ホモジナイザーに３００ｋｇ／ｃｍ
2 の圧力で２回通し、乳化組成物を得た。得られた乳化
組成物について下記の試験を行った。結果を表１に示
す。90.0 g of fluorine-containing siloxane represented by
Was gradually added and mixed uniformly with a homomixer. Transfer the resulting mixture to a 500 ml plastic beaker,
171.0 g of water was gradually added to this to obtain a dispersion liquid.
Then, add this to a high pressure homogenizer at 300 kg / cm.
It was passed twice under a pressure of 2 to obtain an emulsified composition. The following tests were performed on the obtained emulsified composition. The results are shown in Table 1.
【００１９】（１）乳化組成物の粘度 ＪＩＳ Ｚ ８８０３に準拠し、２５℃における粘度を
測定した。 （２）保存安定性試験 １００ｍｌのガラス瓶に乳化組成物１００ｇを入れて蓋
をし、４５℃で７日間静置した後、外観を目視によって
観察して以下の基準で評価した。 ○： 分離なし（液表面にオイル浮きなし） △： 分離なし（液表面にオイル浮きあり） ×： 分離あり （３）希釈安定性試験 １５０ｍｌのプラスチックビーカーに乳化組成物２ｇを
入れた後、水９８ｇで希釈して蓋をし、２５℃で２２時
間静置した後、外観を目視によって観察し、以下の基準
で評価した。 ○： 分離なし ×： 分離あり(1) Viscosity of Emulsion Composition The viscosity at 25 ° C. was measured according to JIS Z8803. (2) Storage stability test 100 g of the emulsified composition was placed in a 100 ml glass bottle, the lid was covered, and the mixture was allowed to stand at 45 ° C. for 7 days. Then, the appearance was visually observed and evaluated according to the following criteria. ◯: No separation (no oil floating on the liquid surface) △: No separation (oil floating on the liquid surface) ×: Separation (3) Dilution stability test After adding 2 g of the emulsion composition to a 150 ml plastic beaker, water The mixture was diluted with 98 g, covered with a lid, allowed to stand at 25 ° C. for 22 hours, and then visually observed for appearance, and evaluated according to the following criteria. ○: No separation ×: Separation
【００２０】（４）撥油性テスト 乳化組成物の２％水溶液をガーゼでアルミ板（５０×１
５０ｍｍ）に塗布し、風乾した後、１３０℃で３０分間
加熱処理をした。室温まで放冷した後、ｎ−ヘプタンを
塗ってはじきの状態を目視によって観察し、以下の基準
で評価した。 ○： はじき点が５０点以上 ×： はじき点が５０点未満 （５）動摩擦係数試験 ＰＥＴ樹脂をコーティングした紙に、実施例１〜４で調
製した乳化組成物をガーゼを用いて均一に塗布し、これ
を１０５℃で３０分間乾燥させた。次に、この紙の上
に、３×４ｃｍのＳＢＲゴムを載せ、該ゴムの背に２０
０ｇのおもりで荷重をかけて該ゴムを摺動させ、このと
きの動摩擦係数をオートグラフを用いて測定した。(4) Oil repellency test A 2% aqueous solution of the emulsified composition was applied to an aluminum plate (50 × 1) with gauze.
50 mm), air dried, and then heat-treated at 130 ° C. for 30 minutes. After allowing to cool to room temperature, n-heptane was applied and the repellency was visually observed and evaluated according to the following criteria. ◯: Repelling point is 50 points or more. ×: Repelling point is less than 50 points. This was dried at 105 ° C. for 30 minutes. Next, put 3 × 4 cm SBR rubber on this paper and put 20 on the spine of the rubber.
The rubber was slid by applying a load with a weight of 0 g, and the dynamic friction coefficient at this time was measured using an autograph.
【００２１】（６）離型性試験 表面にクロームめっきした４×１２ｃｍのテストピース
に、実施例１〜４で調製した乳化組成物をガーゼを用い
て均一に塗布し、これを１０５℃で３０分間乾燥させ
た。次に、この上にパーオキサイド加硫型フッ素ゴム
（ダイキン工業（株）製、ダイエルＧ−９０２）を配置
し、この上から１５０℃で１０分間プレス加硫し、次い
で、これを１８０℃で４時間オーブン加硫した。この加
硫されたゴム片について以下の基準で離型性を評価し
た。 ○・・・ほとんど力を加えずになめらかに離型した。 △・・・少し力を加えるとなめらかに離型した。 ×・・・かなり力を加えないと離型しなかった。(6) Releasability test The emulsified compositions prepared in Examples 1 to 4 were uniformly applied to a chrome-plated 4 × 12 cm test piece using gauze, and this was tested at 105 ° C. for 30 minutes. Allow to dry for minutes. Next, a peroxide vulcanizing fluororubber (Daikin Industry Co., Ltd., Daiel G-902) was placed on this, and press vulcanization was performed from above on at 150 ° C. for 10 minutes, and then at 180 ° C. Oven vulcanization for 4 hours. The releasability of this vulcanized rubber piece was evaluated according to the following criteria. ○: The mold was released smoothly with almost no force applied. Δ: The mold was released smoothly by applying a little force. ×: The mold was not released unless a considerable amount of force was applied.
【００２２】実施例２ 実施例１で用いた（Ｂ）成分に代え、ＨＬＢ値が１８．
０のポリオキシエチレン２級アルキルエーテル（但し、
アルキルは炭素原子数１２〜１４である）４．２ｇと、
ＨＬＢ値が１０．５のポリオキシエチレン２級アルキル
エーテル（但し、アルキルは炭素原子数１２〜１４であ
る）４．８ｇとを用いた他は、実施例１と同様の方法で
乳化組成物を得た。得られた乳化組成物について実施例
１と同様の試験を行った。結果を表１に示す。 Example 2 In place of the component (B) used in Example 1, the HLB value was 18.
0 polyoxyethylene secondary alkyl ether (however,
Alkyl has 12 to 14 carbon atoms) 4.2 g,
An emulsion composition was prepared in the same manner as in Example 1 except that 4.8 g of a polyoxyethylene secondary alkyl ether having an HLB value of 10.5 (wherein alkyl has 12 to 14 carbon atoms) was used. Obtained. The same test as in Example 1 was performed on the obtained emulsified composition. The results are shown in Table 1.
【００２３】実施例３ 実施例１で用いた（Ｂ）成分に代え、ＨＬＢ値が１５．
０のポリオキシエチレンソルビタンモノオレエート８．
２ｇと、ＨＬＢ値が４．３のポリオキシエチレンソルビ
タンモノオレエート０．８ｇとを用いた他は、実施例１
と同様の方法で乳化組成物を得た。得られた乳化組成物
について実施例１と同様の試験を行った。結果を表１に
示す。実施例４ 実施例１で用いた（Ａ）成分に代え、下記式： Example 3 In place of the component (B) used in Example 1, the HLB value was 15.
0 polyoxyethylene sorbitan monooleate 8.
Example 1 except that 2 g and 0.8 g of polyoxyethylene sorbitan monooleate having an HLB value of 4.3 were used.
An emulsified composition was obtained in the same manner as in. The same test as in Example 1 was performed on the obtained emulsified composition. The results are shown in Table 1. Example 4 Instead of the component (A) used in Example 1, the following formula:
【００２４】[0024]
【化５】 Embedded image
【００２５】で表される含フッ素シロキサン９０．０ｇ
を用いた他は、実施例１と同様の方法で乳化組成物を得
た。得られた乳化組成物について実施例１と同様の試験
を行った。結果を表１に示す。90.0 g of fluorine-containing siloxane represented by
An emulsion composition was obtained in the same manner as in Example 1 except that the above was used. The same test as in Example 1 was performed on the obtained emulsified composition. The results are shown in Table 1.
【００２６】比較例 実施例１で用いた（Ａ）成分に代え、２５℃における粘
度が３５０ｃＳｔのジメチルポリシロキサン９０．０ｇ
を用い、実施例１で用いた（Ｂ）成分に代え、ＨＬＢが
６．０のポリオキシエチレンオクチルフェニルエーテル
３．４２ｇ及びＨＬＢが１７．５のポリオキシエチレン
ノニルフェニルエーテル６．８７ｇ及びポリオキシエチ
レントリデシルエーテル硫酸ナトリウム（エチレンオキ
シド５モル付加物）１．０２ｇを用い、（Ｃ）成分とし
て水１９８．７ｇを用いた他は、実施例１と同様の方法
で乳化組成物を得た。得られた乳化組成物について実施
例１と同様の試験を行った。結果を表１に示す。 Comparative Example 90.0 g of dimethylpolysiloxane having a viscosity at 25 ° C. of 350 cSt in place of the component (A) used in Example 1.
In place of the component (B) used in Example 1, 3.42 g of polyoxyethylene octyl phenyl ether having an HLB of 6.0 and 6.87 g of polyoxyethylene nonyl phenyl ether having an HLB of 17.5 and polyoxy An emulsified composition was obtained in the same manner as in Example 1 except that 1.02 g of sodium ethylene tridecyl ether sulfate (5 mol adduct of ethylene oxide) was used and 198.7 g of water was used as the component (C). The same test as in Example 1 was performed on the obtained emulsified composition. The results are shown in Table 1.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】本発明によると、低粘度でかつ、保存安
定性、希釈安定性に優れると同時に、取扱において、作
業安全性及び環境保全性に優れ、水系で使用する場合に
も、優れた撥油性、離型性、潤滑性、洗浄性を発揮する
乳化組成物が提供される。EFFECTS OF THE INVENTION According to the present invention, it has a low viscosity and is excellent in storage stability and dilution stability, and at the same time, it is excellent in work safety and environmental conservation in handling, and is excellent even when used in an aqueous system. There is provided an emulsified composition exhibiting oil repellency, mold releasability, lubricity and detergency.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井口 良範 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社シリコーン電子材料 技術研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoshinori Iguchi 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory
Claims (2)
ロオキシアルキル基であり、Ｍｅはメチル基であり、Ｌ
は０又は１の整数であり、ｍは４〜２０の整数であり、
ｎは１〜３の整数である）で表される含フッ素シロキサ
ン、（Ｂ）界面活性剤、及び（Ｃ）水を含有する含フッ
素シロキサン水中油滴型組成物。1. (A) The following general formula (1): (In the formula, Rf is a perfluoroalkyl group or a perfluorooxyalkyl group, Me is a methyl group, and L is
Is an integer of 0 or 1, m is an integer of 4 to 20,
n is an integer of 1 to 3) A fluorine-containing siloxane oil-in-water composition containing a fluorine-containing siloxane represented by the formula (B), a surfactant (B), and water (C).
０〜１８のノニオン界面活性剤である請求項１に記載の
含フッ素シロキサン水中油滴型組成物。2. The (B) surfactant has an HLB value of 1
The fluorinated siloxane oil-in-water composition according to claim 1, which is a nonionic surfactant of 0 to 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33432994A JP3178980B2 (en) | 1994-12-16 | 1994-12-16 | Fluorinated siloxane oil-in-water emulsion composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33432994A JP3178980B2 (en) | 1994-12-16 | 1994-12-16 | Fluorinated siloxane oil-in-water emulsion composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08170020A true JPH08170020A (en) | 1996-07-02 |
| JP3178980B2 JP3178980B2 (en) | 2001-06-25 |
Family
ID=18276146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33432994A Expired - Fee Related JP3178980B2 (en) | 1994-12-16 | 1994-12-16 | Fluorinated siloxane oil-in-water emulsion composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3178980B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006107082A3 (en) * | 2005-04-01 | 2007-01-25 | Daikin Ind Ltd | Surface modifier and its use |
| EP3040385A1 (en) * | 2013-08-28 | 2016-07-06 | Dipsol Chemicals Co., Ltd. | Friction modifier for top coating agent for trivalent chromium chemical conversion coating film or chromium-free chemical conversion coating film, and top coating agent including same |
| CN108752590A (en) * | 2018-04-25 | 2018-11-06 | 中科广化（重庆）新材料研究院有限公司 | A kind of long-chain siloxy flucride siloxane lotion and its modified inorganic silicate coating and preparation method thereof |
-
1994
- 1994-12-16 JP JP33432994A patent/JP3178980B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006107082A3 (en) * | 2005-04-01 | 2007-01-25 | Daikin Ind Ltd | Surface modifier and its use |
| US8664421B2 (en) | 2005-04-01 | 2014-03-04 | Daikin Industries, Ltd. | Surface modifier and its use |
| EP3040385A1 (en) * | 2013-08-28 | 2016-07-06 | Dipsol Chemicals Co., Ltd. | Friction modifier for top coating agent for trivalent chromium chemical conversion coating film or chromium-free chemical conversion coating film, and top coating agent including same |
| EP3040385A4 (en) * | 2013-08-28 | 2017-03-29 | Dipsol Chemicals Co., Ltd. | Friction modifier for top coating agent for trivalent chromium chemical conversion coating film or chromium-free chemical conversion coating film, and top coating agent including same |
| US9650521B1 (en) | 2013-08-28 | 2017-05-16 | Dipsol Chemicals Co., Ltd. | Friction modifier for top coating agent for trivalent chromium chemical conversion coating film or chromium-free chemical conversion coating film, and top coating agent including same |
| CN108752590A (en) * | 2018-04-25 | 2018-11-06 | 中科广化（重庆）新材料研究院有限公司 | A kind of long-chain siloxy flucride siloxane lotion and its modified inorganic silicate coating and preparation method thereof |
| CN108752590B (en) * | 2018-04-25 | 2021-08-13 | 中科广化（重庆）新材料研究院有限公司 | Long-chain silicon-oxygen-based fluorine-containing siloxane emulsion, modified inorganic silicate coating thereof and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3178980B2 (en) | 2001-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100537391B1 (en) | Water Dispersible Antifoam Concentrates | |
| CA2191507C (en) | Polysiloxane-polyoxyethylene-polyoxypropylene triblock copolymers and defoaming compounds containing them | |
| EP0550915A1 (en) | Water-repellent emulsion composition and process for the production thereof | |
| KR20100007709A (en) | Membrane curing agent for a cement structure | |
| US7544734B2 (en) | Silicone oil-in-water (O/W) emulsion compositions useful for water repellent applications | |
| JPH08170020A (en) | Fluorine-containing siloxane o/w-type emulsion composition | |
| CN113604096B (en) | Fluorocarbon wetting agent compound system | |
| WO2015193649A1 (en) | Aqueous composition for cleaning or removing coatings | |
| MXPA01005807A (en) | Stable aqueous emulsions of nonpolar silanes having constant particle size. | |
| EP2895565A1 (en) | Clear microemulsion stripping formulations | |
| AU753133B2 (en) | Stable, constant particle size, aqueous emulsions of nonpolar silanes suitable for use in water repellence applications | |
| JP2005054090A (en) | Oil-in-water type modified silicone emulsion composition | |
| CZ161795A3 (en) | Neutral self-polishing emulsion for treating floors | |
| JP4717435B2 (en) | Silicone emulsion composition and mold release agent | |
| JPH05295264A (en) | Oil-in-water type emulsion composition for paintable mold release agent | |
| JP2004035820A (en) | Silicone emulsion composition and releasing agent | |
| CA2097415A1 (en) | Lithographic Dampening Solution | |
| JP2021185218A (en) | Anti-sticking agent composition for unvulcanized rubber, aqueous dispersion liquid of anti-sticking agent composition for unvulcanized rubber, and unvulcanized rubber | |
| JPH05279657A (en) | Water-repelling emulsion composition and its production | |
| EP0620249A1 (en) | Silicone emulsion | |
| JP2023075023A (en) | Anti-adhesion composition for unvulcanized rubber, anti-adhesion composition moisture dispersant for unvulcanized rubber, and unvulcanized rubber | |
| KR100553341B1 (en) | Magnesium Stearate Anti-tack agent of Environmentally friendly for Rubber sheets | |
| WO2021235334A1 (en) | Water repellent composition and fiber treatment agent | |
| MXPA01005800A (en) | Stable, constant particle size, aqueous emulsions of nonpolar silanes suitable for use in water repellence applications | |
| MXPA98004061A (en) | Concentrates dispersible antispumants in a |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |